CN103732393B - Duplexer, gas barrier film, the manufacture method of duplexer and laminated body producing device - Google Patents

Duplexer, gas barrier film, the manufacture method of duplexer and laminated body producing device Download PDF

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CN103732393B
CN103732393B CN201280037062.9A CN201280037062A CN103732393B CN 103732393 B CN103732393 B CN 103732393B CN 201280037062 A CN201280037062 A CN 201280037062A CN 103732393 B CN103732393 B CN 103732393B
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film
duplexer
ald
layer
atomic layer
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CN103732393A (en
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吉原俊昭
黑木恭子
加纳满
佐藤尽
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Toppan Inc
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Toppan Printing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]

Abstract

The present invention provides a kind of duplexer, it is characterized in that, comprising: base material (2), outer surface along base material (2) formed atomic layer deposition film (4), with the mechanical strength film higher than atomic layer deposition film (4) to cover the seal coat (5) of atomic layer deposition film (4).

Description

Duplexer, gas barrier film, the manufacture method of duplexer and laminated body producing device
Technical field
The present invention relates to be formed with the duplexer of atomic layer deposition film at the outer surface of base material, formed based on this duplexer Gas barrier film (gas barrier film), be formed with the manufacture method of the duplexer of atomic layer deposition film at the outer surface of base material And for manufacturing the laminated body producing device of this duplexer.
The application advocates based on " Patent 2011-165903 ", " Patent 2011-proposed to Japan on July 28th, 2011 No. 165904 " priority applied for, and its content is incorporated herein.
Background technology
About material is formed be used with the gas phase of the state of atom/molecule horizontal movement as gas with The method forming thin film on the surface of object, substantially divides into chemical vapour deposition technique (CVD:Chemical Vapor And physical vaporous deposition (PVD:Physical Vapor Deposition) Deposition).
As in the representational method of PVD, there are vacuum vapour deposition or sputtering method etc., particularly for sputtering method, Under normal circumstances, although installation cost is high, but owing to film quality and the excellent high quality thin film of film thickness uniformity can be implemented Film forming, therefore, is widely used in the display device etc. of liquid crystal display etc..
It addition, CVD is to import in vacuum chamber by unstrpped gas, make one or more gas at base by thermal energy Decompose on plate or react and the method that makes solid film grow.Now, in order to promote film forming reaction time or in order to reduce reaction Temperature, the method also having and reacting with plasma, catalyst (Catalyst), it is known respectively as PECVD(Plasma Enhanced CVD, plasma enhanced chemical vapor deposition method), Cat-CVD(catalytic chemical vapor deposition technique) etc..Above-mentioned CVD has the feature that film forming defect is few, in the manufacturing process of the semiconductor device such as film forming being mainly used in gate insulating film.
It addition, atomic layer deposition method (ALD: Atomic Layer Deposition) receives publicity in recent years.This ALD Method be a kind of material making surface adsorption by the chemical reaction on surface with the method for atomic level successively film forming, be classified as The category of CVD.Additionally, the difference of ALD and common CVD is, the so-called common CVD of CVD() be use single gas or The method that person uses multiple gases to react on substrate simultaneously and makes thin film grow.In contrast, ALD is alternately to use Presoma (TMA:Tri-Methyl Aluminum(trimethyl aluminium)) or it is referred to as the rich of precursor (precursor) The gas of activity and reactant gas (this in ALD also referred to as presoma), by substrate surface absorption and with Generation chemical reaction and make the special film build method that thin film successively grows with atomic level.
The concrete film build method of ALD is, in the surface adsorption on substrate, once surface is covered by certain gas, Then will not occur this gas is adsorbed greatly, to above-mentioned so-called from limit (self-limiting) effect add in order to With, when only adsorbing the presoma of a layer, just unreacted presoma is exhausted.Then, import reactant gas, make elder generation Before oxidation of precursor or reduction and after only obtaining one layer of thin film with required composition, reactant gas is exhausted. It is a circulation with above-mentioned process, repeats this circulation so that thin film growth is gone down.Therefore, in ALD thin film be bidimensionality enter Row growth.It addition, ALD is compared with conventional vacuum vapour deposition or sputtering method etc., advantage is self-evident, even if with common CVD etc. compare, it may have the feature that film forming defect is few.Therefore, expect to be applied to the packaging field of food and medicine product etc. Or in the field widely such as electronic component field.
It addition, in ALD, decomposing the second presoma and reacting with the absorption the first presoma on substrate In operation, in order to make reaction activate, the method having using plasma.The method is referred to as plasma enhanced atomic layer deposition (PEALD:Plasma Enhanced ALD) method or referred to as Plasma-Atomic layer sedimentation (plasma ALD).
The technology of ALD itself is to be proposed by Mo Sutongla (Tuomo Sumtola) doctor that drags of Finland in 1974 's.High-quality, highdensity film forming can be obtained generally, due to ALD, therefore exist in the semiconductor applications such as gate insulating film Advancing application, at ITRS(International Technology Roadmap for Semiconductors, the world is partly led Body technique blueprint) in also have their record.It addition, ALD, compared with other membrane formation process, there is not oblique shadow owing to having The features such as effect (the oblique phenomenon injecting substrate surface and produce that film forming is uneven of sputter particle), therefore, if there being gas to enter Gap then film forming be possible.Therefore, ALD, except on the substrate of the high-aspect-ratio big at the ratio with depth and width Wire or poroid overlay film beyond, be also expected to be applied in the overlay film purposes of three-dimensional structure and MEMS(Micro Electro Mechanical Systems, MEMS) related aspect etc..
But, ALD also has shortcoming.Use the shortcoming of special material i.e., it is possible to enumerate for implementing ALD, thus lead The shortcomings such as the cost up caused, maximum shortcoming is that film forming speed is slow.Such as, with membrane formation process such as common vacuum evaporation or sputters Compare, the degree that film forming speed is the most about 5～10 times.
For using above-described membrane formation process to form the object of thin film according to ALD, exist following various Substrate: plate-like substrate as small-sized in wafer or photomask etc., such as large area such as glass plates and without flexible substrate, or, such as film (film) large area and have the substrate etc. of flexibility such as.These purposes corresponding, for criticizing of being formed on these substrates by thin film Amount production equipment aspect, has people according to cost, processing ease degree and to become film quality etc., it is proposed that the behaviour of various substrates Make method and to make it obtain practical.
Such as, in the case of a wafer, there is following film formation device: a plate base supply become to film formation device Film, then displaces a plate base and carries out the one chip film formation device of film forming again；Multi-piece substrate is collected assembling, to all Wafer carry out unifying the batch film formation device etc. of film forming.
It addition, in the example carrying out film forming for glass substrate etc., have a kind of online (in-line) film formation device, It is to carry out film forming while relative to the part as film deposition source successively conveying substrate.And, also have a kind of with what is called volume The film formation device that volume mode is coated, it is primarily directed to flexible substrate, is unclamped by substrate, carries from roller, and one While carry out film forming and substrate be wound on other roller.In the latter, also include a kind of takeup type coating (Web coating) film forming Device, it is not only for flexible substrate, but also can will be placed on scratching of can carrying continuously as the substrate of film forming object Property lamellar body or local for carrying out continuous film forming on flexible pallet.
For the film build method or substrate operational approach of any one film formation device, also from becoming present aspect, quality, operation to hold Easily degree is angularly set out and is judged, thus uses the combination of the fastest film formation device of film forming speed.
Additionally, as corresponding technology, disclose a kind of by carry out ald according to ALD and at plastic base or The technology (for example, referring to patent documentation 1) on gas permeation barrier layer is formed on person's glass substrate.Based on this technology, scratch having Property and photopermeability plastic base on load light emitting polymer, and according to ALD in the surface of this light emitting polymer and side Implement ald (carrying out topcoating (top coating)).Thus, coating defects can not only be reduced, and be capable of A kind of barrier film of the photopermeability that on the thickness of tens nanometers, gas permeation can be significantly decreased.
Further, as other corresponding technology, one has been also disclosed and has related to use ALD to be formed on substrate and stop The technology (for example, referring to patent documentation 2) of the barrier layer process unit of layer.Based on this technology, by by film (film) shape substrate It is loaded on conveyer belt thus in the through flowing being displaced in vacuum chamber, the substrate surface that conveyer belt is loaded is formed former Sublayer deposition film.And then, film (film) the shape substrate that will be formed with atomic layer deposition film is wound on winding drum, thus carries out The film (film) that high-speed production gas barrier property is high.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2007-516347 publication
Patent documentation 2: Japanese Unexamined Patent Application Publication 2007-522344 publication
Summary of the invention
The problem that invention is to be solved
As it has been described above, since Yi Wang, it is provided with the layer of atomic layer deposition film at the outer surface of base material (substrate) according to ALD Stack is well known, and these duplexers are preferably applied to the gas barrier film with gas barrier property.But, atomic layer deposition film exists and holds The problem easily producing scar under the effects such as external force.If atomic layer deposition film produce scar, then sometimes according to scar size and Produce and extend the through hole on the film thickness direction of atomic layer deposition film.If so film thickness direction is produced at atomic layer deposition film Through hole, then gas can be caused to pass this through hole and to come in and go out, therefore cause gas barrier property to reduce.
Therefore, when manufacturing the duplexer with the atomic layer deposition film the most easily producing scar, it is being formed with atom After layer deposition film, if not the production line making this atomic layer deposition film not contact with rigid body (rigid body), then can become resistance The main cause that gas reduces.It is therefoie, for example, in the case of manufacturing film (film) shape duplexer (that is, gas barrier film), work as employing When gas barrier film is wound into roll by take-up roll, it is possible to the atomic layer deposition film at substrate surface produces scar, causes gas barrier property Reduce.That is, from the viewpoint of keeping high-gas resistance, carry out after gas barrier film being wound into roll in the manufacturing process of duplexer Conveying or keeping aspect existing problems.
Additionally, for barrier film (barrier film) disclosed in patent documentation 1, though being silent on manufacturer Method, but when film (film) shape substrate (base material) is wound in winding drum by technology disclosed in using such as patent documentation 2, Likely in the same manner as aforementioned, atomic layer deposition film is produced scar, therefore, it is difficult to keep high-gas resistance.
The present invention completes in view of the foregoing, its object is to provide: it is former that the outer surface at base material is formed Sublayer deposition film easily will not cause scar under external force thus improve the duplexer of gas barrier property；Formed by this duplexer Gas barrier film；The manufacture method of aforementioned layers stack；And for manufacturing the laminated body producing device of aforementioned layers stack.
The method solving problem
The 1st aspect of the present invention is a kind of duplexer, it is characterised in that comprising: base material；Outside aforementioned substrates The atomic layer deposition film that surface is formed；And, cover atomic layer deposition with the film that mechanical strength is higher than aforementioned atomic layer deposition film The seal coat of integrated membrane.
The 2nd aspect of the present invention is a kind of duplexer, it is characterised in that comprising: base material；Outside aforementioned substrates The atomic layer deposition film that surface is formed；And, to have the mechanical strength identical with aforementioned atomic layer deposition film and Film Thickness Ratio The film of aforementioned ald thickness covers the seal coat of this atomic layer deposition film.
Furthermore it is possible to stop that coated body forms aforementioned seal coat by water system.
It addition, aforementioned water system stop coated body can have in OH base and COOH base at least any one.
It addition, aforementioned seal coat, inorganic substances can be contained.
It addition, the duplexer of above-mentioned first and second modes, can between aforementioned substrates and aforementioned atomic layer deposition film, Also there is the priming coat being dispersed with the inorganic substances being combined with aforementioned atomic layer deposition film.
It addition, the duplexer of above-mentioned first and second modes, it is characterised in that at aforementioned substrates and aforementioned ald Between film, also have containing the organic macromolecule priming coat being combined with aforementioned atomic layer deposition film.
The 3rd aspect of the present invention is a kind of gas barrier film, it is characterised in that it has above-mentioned first method or above-mentioned second The duplexer of mode, and above-mentioned duplexer is formed as film (film) shape.
The 4th aspect of the present invention is the manufacture method of a kind of duplexer, it is characterised in that comprising: the first operation, should Operation is along the atomic layer deposition film of the outer surface forming film shape of base material；Second operation, this operation is being in and described first In online (the in line) of the in-process of operation series connection, along the outer surface of described atomic layer deposition film, form mechanical strength ratio The seal coat that this atomic layer deposition film is high, generation layer stack；And, the 3rd operation, this operation is with shape in described second operation The seal coat become carries out the mode contacted with rigid body, receives described duplexer.
The 5th aspect of the present invention is the manufacture method of a kind of duplexer, it is characterised in that comprising: the first operation, should Operation is along the atomic layer deposition film of the outer surface forming film shape of base material；Second operation, this operation is being in and described first Operation series connection in-process online in, along the outer surface of described atomic layer deposition film, to have and described ald Mechanical strength and the film of this ald thickness of Film Thickness Ratio that film is identical form seal coat, generation layer stack；And, 3rd operation, in the way of the seal coat that this operation is formed in described second operation contacts with rigid body, receives described layer Stack.
The 6th aspect of the present invention is the manufacture method of a kind of duplexer, it is characterised in that comprising: the first operation, should Operation, along the outer surface of base material, forms the priming coat containing at least one in inorganic substances and organic polymer；Second work Sequence, this operation with in the inorganic substances that expose on the surface of the priming coat formed in described first operation and organic polymer The mode that is combined of at least one, at the atomic layer deposition film of the outer surface forming film shape of described priming coat；3rd work Sequence, this operation be in the in-process connected with described second operation online in, along the appearance of described atomic layer deposition film Face, forms the seal coat that mechanical strength is higher than this atomic layer deposition film, generation layer stack；And, the 4th operation, this operation with The seal coat formed in described 3rd operation carries out the mode contacted with rigid body, receives described duplexer.
The 7th aspect of the present invention is the manufacture method of a kind of duplexer, it is characterised in that comprising: the first operation, should Operation, along the outer surface of base material, forms the priming coat containing at least one in inorganic substances and organic polymer；Second work Sequence, this operation with in the inorganic substances that expose on the surface of the priming coat formed in described first operation and organic polymer The mode that is combined of at least one, at the atomic layer deposition film of the outer surface forming film shape of described priming coat；3rd work Sequence, this operation be in the in-process connected with described second operation online in, along the appearance of described atomic layer deposition film Face, is formed having the film of the mechanical strength identical with described atomic layer deposition film and this ald thickness of Film Thickness Ratio Seal coat, generation layer stack；And, the 4th operation, this operation is with the seal coat formed in described 3rd operation and rigid body Carry out the mode contacted, receive described duplexer.
It addition, described rigid body is take-up roll, after described 3rd operation or described 3rd operation, can be by described duplexer Carry out contacting with described take-up roll in roll mode thus wind, receive this duplexer.
It addition, described seal coat, can be to use flash distillation vapour deposition method by acrylic acid film forming in described atomic layer deposition film The layer of outer surface.
It addition, described seal coat, can be formed with chemical vapour deposition technique.
The 8th aspect of the present invention is a kind of laminated body producing device, its will be formed as thin plate, thin slice (film, film) or On membranaceous banding substrate, film forming has the duplexer of atomic layer deposition film, at online in-process, carries out defeated in volume to volume mode Send, it is characterised in that comprising: supporting mass, this supporting mass supports in a thickness direction face of described base material；Conveyer Structure, described base material is carried in one direction by this conveying mechanism along the outer surface of described supporting mass；Ald film forming portion, This ald film forming portion is so that described base material inserts between this ald film forming portion and outer surface of described supporting mass Mode configure, and make described atomic layer deposition film film forming in another face in a thickness direction of this base material；Cover and be coated with Cloth body forming portion, the described ald film forming portion that this covering coated body forming portion is arranged on the conveying direction of described base material Downstream, the surface of described atomic layer deposition film formed mechanical strength stronger than described atomic layer deposition film or Film Thickness Ratio The seal coat of this ald thickness；And, winding mechanism, this winding mechanism is arranged on the conveying direction of described base material The downstream of described covering coated body forming portion, as contact surface, described duplexer is wound into roll using described seal coat.
It addition, described covering coated body forming portion, can be to be deposited with by flash distillation or cover described in chemical gaseous phase formation of deposits Lid coating.
It addition, the laminated body producing device of above-mentioned eighth mode, it may additionally include on the conveying direction of described base material It is configured at the primary coat forming portion of upstream, described ald film forming portion, and, described primary coat forming portion, in described base material appearance Face forms the priming coat with the binding site being combined with described atomic layer deposition film.
Invention effect
The duplexer of the present invention and the gas barrier property of gas barrier film are high.It addition, the manufacture method of the duplexer of the present invention and stacking System manufacturing apparatus, it is possible to be easily manufactured the duplexer that gas barrier property is high.
Accompanying drawing explanation
Fig. 1 is the profile of the structure of the duplexer representing first embodiment of the invention.
Fig. 2 is the profile of the structure of the duplexer representing second embodiment of the invention.
Fig. 3 is the duplexer to the present embodiment having seal coat and the duplexer of the comparative example without seal coat carries out water The figure of the comparison of vapor transmission rates.
Fig. 4 is the duplexer manufacture being formed seal coat by flash distillation vapour deposition method being applied to third embodiment of the invention The summary construction diagram of device.
Fig. 5 is the laminated body producing device being formed seal coat by CVD being applied to four embodiment of the invention Summary construction diagram.
Fig. 6 is the stream summarizing the manufacturing process of duplexer when being not provided with priming coat in embodiment of the present invention Cheng Tu.
Fig. 7 is the stream summarizing the manufacturing process of duplexer when being provided with priming coat in embodiment of the present invention Cheng Tu.
Fig. 8 is the duplexer to the present embodiment having seal coat and the duplexer of the comparative example being not provided with seal coat enters The figure of the comparison of row moisture-vapor transmission (WVTR).
Detailed description of the invention
" summary of embodiment "
The duplexer of embodiments of the present invention, substantially forms following structure: be formed with atom on the surface of base material Layer deposition film, and then it is formed with seal coat in the way of covering this atomic layer deposition film surface.As long as this seal coat might as well Hinder the characteristic of base material, ALD film, then can be the layer with any characteristic.Additionally, for generating in thickness side in seal coat External force size needed for the through hole extended, needs higher than for generating on atomic layer deposition film in film thickness direction extension External force size needed for through hole.In other words, needing seal coat is the film higher than the mechanical strength of atomic layer deposition film.Or Person, in the case of seal coat has the mechanical strength identical with atomic layer deposition film, then needing seal coat is to be thicker than The layer that the thickness of atomic layer deposition film is formed.
Additionally, the duplexer of embodiment of the present invention, it is also possible to there is between base material and atomic layer deposition film priming coat. I.e., it is also possible to be following structure: substrate surface formed priming coat, and then base coating surface formed atomic layer deposition film, with The mode covering this atomic layer deposition film surface forms seal coat.
" the 1st embodiment "
Fig. 1 is the profile of the structure of the duplexer representing first embodiment of the invention.As it is shown in figure 1, first implements The duplexer 1a of mode has a following structure: the base material 2 formed with macromolecular material；Be formed as membranaceous on the surface of base material 2 Atomic layer deposition film (calling " ALD film " in the following text) 4；And, cover covering of this ALD film 4 with the film that mechanical strength is higher than ALD film 4 Lid coating (calling " OC layer " in the following text) 5.Additionally, OC layer 5 can also have the mechanical strength identical with ALD film 4 and with Film Thickness Ratio ALD The film of film 4 thickness covers this ALD film 4.
That is, if by OC layer 5 film forming higher than ALD film 4 for mechanical strength in the surface of ALD film 4, causing even if being then applied with ALD film 4 produces scar and produces the External Force Acting of the degree size of through hole on film thickness direction, and OC layer 5 also will not be made because of this The external force of degree and produce through hole at film thickness direction.Therefore, based on by OC layer 5 film forming in the surface of ALD film 4, it is possible to increase The gas barrier property of duplexer 1a.It addition, when film forming has the OC layer 5 of the mechanical strength identical with ALD film 4, if with Film Thickness Ratio ALD The film of film 4 thickness carrys out film forming OC layer 5, even if then making ALD film 4 produce scar and produce through hole at film thickness direction, also will not make OC Layer 5 produces through hole because of the external force of this degree at film thickness direction.Therefore, it is possible to improve the gas barrier property of duplexer 1a.
Additionally, OC layer 5 is to stop that coated body is formed by water system, this water system stops coated body, and its functional group has OH Base or COOH base.It addition, OC layer 5 can also contain inorganic substances.Water system stops coated body, is by by the organic high score of water system The hydrating polymer of the organo-metallic compound compositions such as son, metal alkoxide or silane coupler and their complex institute structure The coated film with block become, can enumerate polyvinyl alcohol, polyacrylic acid, polymine as water system organic polymer Deng.
As organo-metallic compound, having metal alkoxide, it is with general formula R 1(M-OR2) represent.Wherein, Rl, R2 Be carbon number be the organic group of 1～8, M is metallic atom.Additionally, metallic atom M is Si, Ti, Al, Zr etc..
Be Si and with Rl(Si-OR2 as metallic atom M) organo-metallic compound that represents, have tetramethoxy-silicane, Tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, MTMS, MTES, diformazan Base dimethoxysilane, dimethyldiethoxysilane etc..
The organo-metallic compound being Zr as metallic atom M and represent with R1 (Zr-OR2), have tetramethoxy zirconium, four Ethyoxyl zirconium, zirconium tetraisopropoxide (tetraisopropoxy zirconium), tetrabutyl zirconate etc..
Be Ti and with R1(Ti-OR2 as metallic atom M) organo-metallic compound that represents, have titanium tetramethoxide, four Ethanolato-titanium, tetraisopropoxy titanium (tetraisopropoxy titanium), four titanium butoxide etc..
Be Al and with R1(AI-OR2 as metallic atom M) organo-metallic compound that represents, have tetramethoxy aluminum, four Aluminum ethoxide, tetraisopropoxide aluminum, four butoxy aluminum etc..
It addition, as inorganic compound, for the candidate materials when using inorganic substances as inorganic particulate, such as, from In the candidate materials of extender pigment, can enumerate: particle diameter is more than the kaolinic galapectite as one of viscosity mineral, carbonic acid Calcium, silicic acid anhydride, silicate hydrate or aluminium oxide etc..It addition, when using inorganic substances as lamellar compound, can enumerate: people Make clay, fluorophologopite, fluorine four silicon Muscovitum, taincolite, fluorine Vermiculitum, fluorine Strese Hofmann's hectorite. (Fluorohectorite), Strese Hofmann's hectorite. (hectorite), saponite (saponite, サ Port Na イ ト), humite (stevensite), montmorillonite (montmorillonite), beidellite (beidellite), kaolinite (kaolinite) or zinc-aluminium serpentine (fraipontite) etc..
Further, as stratiform viscosity mineral, it is also possible to by pyrophyllite (pyrophyllite), Talcum, montmorillonite (with artificial Clay repeat), beidellite, nontronite (nontronite), saponite, Vermiculitum, sericite (sericite), glauconite, celadonite (seladonite), kaolinite, nacrite (Nacrite), dickite (dickite), galapectite (halloysite), leaf snake Stone (antigorite), choysotile (chrysotile), pictoamesite (amesite), cronstedtite (cronstedite), roe Between chlorite (chamosite), chlorite, rectorite (allevardite), corrensite (Corrensite) or green mud The inorganic substances such as montmorillonite (tosudite) use as lamellar compound.
Additionally, as the inorganic particulate (spherical particle) beyond extender pigment be, as the oxidation of polycrystalline compound The metal-oxide such as zirconium, titanium dioxide, the chemical general formula MM'O such as Barium metatitanate., strontium titanatesXComprising represented by Deng is two or more Metallic atom (M, M ' ...) metal-oxide etc..
" the 2nd embodiment "
Fig. 2 is the profile of the laminate construction representing second embodiment of the invention.As in figure 2 it is shown, the second embodiment party The difference of the duplexer 1a of first embodiment shown in duplexer 1b Yu Fig. 1 of formula, is between base material 2 and ALD film 4 There is this one side of priming coat (calling " UC layer " in the following text) 3.Can also comprise organic high additionally, UC layer 3 both can comprise inorganic substances Molecule.
That is, duplexer 1b includes following structure: with the base material 2 of macromolecular material formation, formed on the surface of base material 2 Membranaceous or the UC layer 3 of thin slice (film: film) shape, the opposition side, face being connected with base material 2 in two faces of the thickness direction of UC layer 3 Face on the ALD film 4 that formed, and cover the OC layer 5 of this ALD film 4 with the film that mechanical strength is higher than ALD film 4.Additionally, OC layer 5 can also have the mechanical strength identical with ALD film 4 and with the film of Film Thickness Ratio ALD film 4 thickness to cover this ALD film 4. Here, comprise organic macromolecule situation owing to the existing situation comprising inorganic substances of UC layer 3 also has, the most respectively both are entered Row explanation.
<comprising the UC layer of inorganic substances>
As in figure 2 it is shown, duplexer 1b has the UC layer 3 being dispersed with inorganic substances between base material 2 and ALD film 4, at ALD The surface of film 4 is formed with OC layer 5.The presoma of ALD film 4 is gas shape material, has and is easily incorporated into UC layer 3 surface and is exposed Inorganic substances on characteristic.Further, on the surface of UC layer 3, owing to substantial amounts of inorganic substances expose, therefore it is incorporated into each inorganic The presoma of the ALD film 4 of material can engage one another while.Thus, the two-dimentional shape of the in-plane growth along UC layer 3 is produced ALD film 4.The gap of gas permeation is allowed, it is possible to realize gas barrier property as a result of which it is, be difficult to produce on the film thickness direction of duplexer 1b High duplexer 1b.
That is, in order to realize (1) raising density of adsorption site of presoma of ALD film 4, the forerunner of (2) prevention ALD film 4 Body spreads this 2 point to polymer base material 2, arranges the UC layer 3 containing inorganic substances on high molecular base material 2.In other words, for The adsorption site making the presoma of ALD film 4 configures on the surface of polymer base material 2 in two dimensions with high density, Before the technique of ALD, the UC layer 3 containing inorganic substances is first set on polymer base material 2.Additionally, in order to improve ALD film 4 Presoma in the density of adsorption site, the adsorption site of the inorganic substances being under high density is used.So carry out Operation, by arranging the UC layer 3 containing inorganic substances (inorganic compound) on polymer base material 2, makes the gas containing presoma Body becomes cannot be through the inorganic substances of UC layer 3.
As it has been described above, the duplexer 1b of the second embodiment, as illustrated in fig. 2, including: the base formed with macromolecular material Material 2, the UC layer 3 of the membranaceous or thin slice formed on the surface of base material 2 (film, film) shape, at two of the thickness direction of UC layer 3 The ALD film 4 formed on the face of the opposition side, face being connected with base material 2 in face, and the OC layer 5 formed on ALD film 4.This Outward, UC layer 3 becomes the structure making an addition in binding agent by inorganic substances (inorganic material).That is, presoma and the UC of ALD film 4 are made Inorganic substances contained in layer 3 are mutually combined, so that ALD film 4 is formed as membranaceous in the way of covering UC layer 3.
Here, the feature of explanation UC layer 3.UC layer 3 is formed by binding agent and inorganic substances (inorganic material).Now, inorganic Material is different from macromolecule and free volume is little.It addition, there is not high molecular glass transition point in inorganic substances, even if therefore In pyroprocess, characteristic also will not change.That is, when macromolecule is more than glass transition point, non-crystallized part starts Blang's fortune Dynamic, the gas diffusion velocity in free volume becomes big, but inorganic substances do not exist and this draw based on glass transition point The phenomenon risen.
It addition, the inorganic substances used by UC layer 3 are lamellar compounds.Therefore, the inorganic substances base of this lamellar compound It is parallel-oriented in the coating surface of base material 2 in basis.It addition, all gas including precursor gas in ALD, nothing Method diffuses to the inside of the inorganic substances of lamellar compound.
Further, in the way of making the surface of the inorganic substances of lamellar compound expose, etch the surface of UC layer 3.That is, for The surface of the inorganic substances of the lamellar compound in the UC layer 3 that exposes on base material 2 import needed for functional group, implement wait from Daughter exposes and etches the surface of UC layer 3.Based on this, the presoma of ALD film 4 can become easily to be incorporated into the inorganic matter of UC layer 3 Matter.
When the UC layer 3 with character described above being arranged at the surface of the most high molecular base material 2, at base material 2 Surface, configures the adsorption site of presoma to high-density.And, make the inorganic substances of lamellar compound in UC layer 3 abreast It is configured at the surface of base material 2.Accordingly, because UC layer 3 covers the surface area of base material 2 almost evenly, therefore make adsorption site with Two-dimensional approach configures, and promotes the two-dimensional growth of ALD film 4.Further, the inorganic substances of the lamellar compound in UC layer 3 Part, even if reaching a high temperature for the technological temperature of the ALD that forms ALD film 4, also will not as plastic macromolecule such Carry out glass transition, therefore can carry out the film growth of stable ALD film 4.
Additionally, the binding agent of UC layer 3 can be organic bond, inorganic bond or the mixing of organic-inorganic binding agent Mixed adhesive in any one.
Duplexer 1b based on said structure, can expose the nothing of lamellar compound on the face of the UC layer 3 on ALD film 4 opposite Machine material, therefore, the presoma of ALD film 4 can be incorporated into the outer surface of these inorganic substances.Particularly, by making inorganic substances shape Granulate or layer structure, it is possible to increase with the adhesion of the presoma of ALD film 4.Further, these inorganic substances are preferably made to be formed as Colloidal sol shape or gelatinous polymer thus obtain optimum adhesion.
It addition, duplexer 1b based on present embodiment, due to the table that can form with arranged in high density functional group Face, therefore, not only in ALD, and in other thin film growth method (such as, vacuum evaporation, sputter, CVD etc.), it is also possible to It is expected that by the high growth pattern of cuclear density and implements the formation of the thin film of densification.
Then, the inorganic compound (inorganic substances) used by UC layer 3 is described in detail.Inorganic substances are following interior by noticing Hold and select.That is, as the selection key element of the inorganic substances constituted according to inorganic particulate, the shape of inorganic particulate connects Torulose particle and the particle of tabular, but also be able to use any one particle.
About the particle size (particle diameter) of inorganic particulate, in order to not affect the flatness of base material 2, set mean diameter as 1 μ Below m, below preferably 0.1 μm.It addition, for the size of inorganic particulate, in order to do one's utmost to avoid it to affect the optics of UC layer 3 Characteristic (that is, light penetration, mist degree (diffusion through light relative to all through the ratio of light)), preferably with the ripple of luminous ray Length compares sufficiently small particle size.Additionally, when inorganic substances are lamellar compounds, selection length-width ratio (Z) (Aspect) is More than 50, thickness is the material of below 20nm.Wherein, mean diameter is being set to L, the thickness of inorganic particulate material is being set to a Time, Z=L/a.
About the optical characteristics of inorganic particulate, go out from the viewpoint carrying out transparent stop coating (barrier coating) Send out, the most preferably colour.Particularly, need to make the binding agent of UC layer 3 and the refractive index of inorganic particulate match.That is, at UC layer 3 In, if the refractive index difference of the refractive index of binding agent and inorganic particulate is big, then the reflection on the interface of UC layer 3 can become big.Its Result is, can cause the reduction of the light penetration of UC layer 3, the increase of mist degree (fuzzy situation).
For the dispersibility of inorganic particulate, because of the good dispersion to binding agent, and it is difficult to cause secondary coagulation.It addition, When inorganic substances are lamellar compounds, it is good with the affinity of binding agent (embedding (Intercalation): chemical bond).
For the stability of inorganic particulate, owing to imagination is 20～30 years when duplexer 1b is used as solar cell Validity period, therefore, even if duplexer 1b life-time service under high temperature, high humidity and extremely low temperature, it is also desirable to inorganic substances are in chemical Can go up stable.Additionally, for the safety of inorganic substances, need in the manufacture process, use of duplexer 1b and discard The all stages processed do not bring harm to environment.
Then, the kind of the inorganic substances added in UC layer 3 is described.For using the inorganic substances used by UC layer 3 as Candidate materials during inorganic particulate, such as, from the candidate materials of extender pigment, can enumerate: particle diameter is more than as viscosity ore deposit Kaolinic galapectite, calcium carbonate, silicic acid anhydride, silicate hydrate or the aluminium oxide etc. of one of thing.It addition, inorganic substances are being made During for lamellar compound, can enumerate: artificial clay, fluorophologopite, fluorine four silicon Muscovitum, taincolite, fluorine Vermiculitum, fluorine Strese Hofmann's hectorite. (Fluorohectorite), Strese Hofmann's hectorite. (hectorite), saponite (saponite, サ Port Na イ ト), humite (stevensite), montmorillonite (montmorillonite), beidellite (beidellite), kaolinite (kaolinite) or Person's zinc-aluminium serpentine (fraipontite) etc..
Further, as stratiform viscosity mineral, it is also possible to by pyrophyllite (pyrophyllite), Talcum, montmorillonite (with artificial Clay repeat), beidellite, nontronite (nontronite), saponite, Vermiculitum, sericite (sericite), glauconite, celadonite (seladonite), kaolinite, nacrite (Nacrite), dickite (dickite), galapectite (halloysite), leaf snake Stone (antigorite), choysotile (chrysotile), pictoamesite (amesite), cronstedtite (cronstedite), roe Between chlorite (chamosite), chlorite, rectorite (allevardite), corrensite (Corrensite) or green mud The inorganic substances such as montmorillonite (tosudite) use as lamellar compound.
Additionally, as the inorganic particulate (spherical particle) beyond extender pigment be, as the oxidation of polycrystalline compound The metal-oxide such as zirconium, titanium dioxide, the chemical general formula MM'O such as Barium metatitanate., strontium titanatesXComprising represented by Deng is two or more Metallic atom (M, M ' ...) metal-oxide etc..
<comprising organic macromolecule UC layer>
As in figure 2 it is shown, duplexer 1b has between base material 2 and ALD film 4 comprises organic macromolecule UC layer 3, at ALD The surface of film 4 is formed with OC layer 5.This UC layer 3 is to comprise organic macromolecule layer, and this organic polymer has and combines ALD film 4 The binding site of presoma.That is, organic polymer contained in UC layer 3 has what easy and ALD film 4 presoma was combined Multiple functional groups as binding site.Therefore, the presoma that functional group each with organic macromolecule is combined is phase each other Combine mutually.Thus, the ALD film 4 of the two-dimentional shape of direction, the face growth along UC layer 3 is produced.As a result of which it is, at the film of duplexer 1b It is difficult on thick direction to produce and allows the gap of gas permeation, it is possible to realize the duplexer 1b that gas barrier property is high.Additionally, in UC layer 3, remove Inorganic substances can also be disperseed beyond organic polymer.That is, by UC layer 3 is added inorganic substances, organic polymer and nothing are made Machine material cooperates, it is possible to improve the adsorption density of the presoma of ALD film 4 further.
That is, in order to realize (1) raising density of adsorption site of presoma of ALD film 4, the forerunner of (2) prevention ALD film 4 Body is diffused this 2 point to polymer base material, can arrange and comprise organic macromolecule UC layer 3 on high molecular base material 2. So, UC layer 3 comprises high-molecular organic material and guarantees the adsorption site of the presoma of ALD film 4.That is, having contained by UC layer 3 Machine macromolecule has the functional group that the presoma of ALD film 4 easily adsorbs.Therefore, having contained by the presoma of ALD film 4 and UC layer 3 The high molecular functional group of machine is combined, and thus makes ALD film be formed as membranaceous in the way of covering UC layer 3.
That is, as in figure 2 it is shown, duplexer 1b includes: the base material 2 formed with macromolecular material, formed on the surface of base material 2 The membranaceous or UC layer 3 of thin slice (flim, film) shape, in two faces of the thickness direction of UC layer 3 with base material 2 connect face contrary The ALD film 4 formed on the face of side, and cover the OC layer 5 on the surface of ALD film 4.UC layer 3 comprise high-molecular organic material and Guarantee the adsorption site of the presoma of ALD film 4.Organic polymer contained by UC layer 3 has the presoma of ALD film 4 and easily adsorbs Functional group.Therefore, the presoma of ALD film 4 is combined with the organic macromolecule functional group contained by UC layer 3, thus makes ALD Film is formed as membranaceous in the way of covering UC layer 3.
Here, owing to guaranteeing the adsorption site on base material 2 by organic polymer contained in UC layer 3, accordingly, it would be desirable to Select the organic polymer with the functional group that the presoma of ALD film 4 easily adsorbs.In addition, it is necessary to select functional group densities high Organic polymer.And then, be preferably based on plasma exposure, hydrolysis process and base material 2 is implemented surface process, thus to having The high molecular modifying surface of machine, make the densification of organic macromolecule functional group.Now, by inorganic compound is added In organic polymer, it is also possible to improve the adsorption density of presoma further.
Additionally, UC layer 3 needs to select to comprise the organic polymer with the functional group that the presoma of ALD film 4 easily adsorbs Material.Such as, when use nylon-6 is as the high-molecular organic material of UC layer 3, owing to functional group is the reason of amide groups, front Drive body and be very easy to absorption, it is therefore preferable that nylon-6 is as the high-molecular organic material used by UC layer 3.On the other hand, the most preferably The polypropylene (PP) etc. with the methyl that presoma is difficult to adsorb is applied to UC layer 3.
That is, if the PP of functional group's (methyl) being difficult to the presoma with ALD film 4 adsorb is applied to priming coat, then ALD The presoma of film is low to the adsorptivity of PP, the ALD film on the border with polymer therefore can be caused to become loose, thus cause choke Property reduce.But, if the nylon-6 of the functional group's (amide groups) easily adsorbed by the presoma with ALD film is applied to primary coat Layer, then the presoma of ALD film is high to the adsorptivity of nylon-6, and therefore the density with the ALD film on the border of polymer uprises, thus Gas barrier property improves.
As the high-molecular organic material of the functional group that the presoma with ALD film 4 easily adsorbs, than that described above, also Including there is the carbamate resins of NCO, there is the polyimide resin of imide, there is the polyethers of sulfuryl Sulfone (PES) and there is the polyethylene terephthalate (PET) etc. of ester group.
Organic macromolecule functional group contained by i.e., preferably UC layer 3 is to have O atom or have the sense of atom N Group.OH base, COOH base, COOR base, COR base, NCO base or SO is had as the functional group with O atom3Base etc..It addition, have There is NH in the functional group of atom NxBase (X is integer).
For the organic polymer of UC layer 3, it is classified as water system and solvent system according to the solvent used.As water system Organic polymer, can enumerate polyvinyl alcohol, polymine etc..It addition, as solvent system organic polymer, third can be enumerated Olefin(e) acid ester, urethane acrylate, polyester acrylate, polyether acrylate etc..
Then, the object lesson that the organic macromolecule used by UC layer 3 is detailed is further illustrated.
1. contain the organic polymer of the resin of O atom
As the organic macromolecule preferred material of the resin containing O atom, it it is material as follows.As containing hydroxyl The resin of base (OH), is polyvinyl alcohol, phenolic resin, polysaccharide etc..Additionally, polysaccharide is cellulose, hydroxymethyl cellulose, hydroxyl The cellulose derivative such as ethyl cellulose, carboxymethyl cellulose, chitin, chitosan etc..It addition, as containing carbonyl (COOH) Resin, the preferably material such as carboxy vinyl polymer (Carboxyvinyl polymer).
As the organic polymer of the resin containing O atom in addition, it is the polyketone of resin containing ketone group (CO), polyethers Ketone, polyether-ether-ketone, aliphatic polyketone etc..It addition, also be able to use containing the polyester resin of resin of ester group (COO), poly-carbonic acid Ester resin, liquid crystal polymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), poly-naphthalene two Formic acid glycol ester (PEN), PBN (PBN), PTT (PTT) etc..Except this it Outward, it is possible to use epoxy system resin containing above-mentioned functional group or acrylic resin etc..
2. contain the organic polymer of the resin of atom N
As the organic macromolecule preferred material of the resin containing atom N, it it is material as follows.Containing acid imide The polyimides of resin of base (CONHCO), Polyetherimide, polyamidoimide, alicyclic polyimides, solvent soluble type Polyimides etc..Additionally, for alicyclic polyimides, generally, aromatic polyimide be by aromatic tetracarboxylic acid's acid anhydride and Aromatic diamine obtains, but owing to without the transparency, as the transparence of polyimides, acid dianhydride or diamidogen can be replaced as Aliphatic or alicyclic.It addition, alicyclic carboxylic acid has 1,2,4,5-cyclopentanetetracarboxylic, 1,2,4,5-Pentamethylene. tetrabasic carboxylic acids two Acid anhydride etc..Further, there are gamma-butyrolacton, N,N-dimethylacetamide, N-methyl-2-pyrrolidine as solvent soluble type polyimides Ketone etc..
It addition, as the organic macromolecule preferred material of the resin containing atom N, also have and set containing amide groups (NHCO) The nylon-6 of fat, nylon-6,6, m-xylene diamine-adipic acid condensed polymer, poly-methyl acrylimide (PMMI) etc..And And, also there is the carbamate resins etc. of resin containing NCO (NHCOO).Additionally, carbamate resins also can Enough use as adhesive layer.In addition, it is also possible to use the resin containing amino (NH).
3. contain the organic polymer of the resin of S atom
The material that can use as the organic polymer of the resin containing S atom, has material as follows.That is, contain There is sulfuryl (SO2) the polyether sulfone (PES) of resin, polysulfones (PSF), polyphenylsulphine (PPS) etc..Wherein, PES and PSF is heat-resisting The material that property is high.Further, polymer alloy, polybutylene terephthalate (PBT) based polymer alloy, polyphenylene sulfide based polymer Alloy etc., it is also possible to use as organic polymer.Additionally, polymer alloy can also make above-mentioned macromolecule as desired Carry out polymer Composite (alloy (alloy), mixing (blend), complex (composite)).
" embodiment "
Then, illustrate to have the specific embodiment of the duplexer of the seal coat realized based on above-mentioned embodiment.First, The common film build method of the gas barrier layer being made up of ALD film is described.Further, illustrate at this when substrate surface forms UC layer The film build method of ALD film.
<film build method of the gas barrier layer being made up of ALD film>
1.Al2O3Film forming
First, use atomic layer deposition method (ALD), arrange on polymeric substrate or on polymeric substrate UC layer above, carry out Al2O3The film forming of film.Now, unstrpped gas is trimethyl aluminium (TMA).It addition, will be as process gas The O of body2And N2It is supplied simultaneously in film forming room with unstrpped gas.It addition, respectively using the O as purge gas2And N2, as reaction Gas is held concurrently the O of plasma process gas2, it is supplied in film forming room.Processing pressure now is set to 10～50Pa.Further, wait from It is the power supply using 13.56MHz that daughter gas excites with power supply, according to ICP(Inductively Coupled Plasma, electricity Sense coupled plasma) pattern enforcement plasma discharge.
It addition, for the service time of each gas, set TMA and process gas as 60 milliseconds of (msec), purge gas Be 10 seconds (sec), reacting gas plasma process gas of holding concurrently be 5 seconds.Then, hold concurrently plasma process at supply response gas While gas, make generation plasma discharge according to ICP pattern.Additionally, now the output of plasma discharge is 250W.It addition, as the purge of gas after plasma discharge, supply 10 seconds purge gas O2And N2.Additionally, film forming now Temperature is 90 DEG C.
Al in cycling condition as above2O3Film forming speed as described below.That is, due to unit film forming speed it is/ circulation, after the film forming implementing to circulate 70 times processes the film forming carrying out 10nm thickness, the total ascent time of film forming is about It it is 30 minutes.
2.TiO2Film forming
First, use ALD, UC layer upper of the surface configuration on polymeric substrate or at polymeric substrate Face, carries out TiO2The film forming of film.Now, unstrpped gas is titanium tetrachloride (TiCl4).It addition, using the N as process gas2With former Material gas is supplied simultaneously in film forming room.It addition, respectively using the N as purge gas2, plasma process of holding concurrently as reacting gas The O of gas2, it is supplied in film forming room.Processing pressure now is set to 10～50Pa.Further, plasma gas excites and uses power supply It is the power supply using 13.56MHz, implements plasma discharge according to ICP pattern.
It addition, for the service time of each gas, set TiCl4With process gas be 60 milliseconds, purge gas be 10 Second, reacting gas plasma process gas of holding concurrently be 3 seconds.Then, hold concurrently the same of plasma process gas at supply response gas Time, make generation plasma discharge with ICP pattern.Additionally, now the output of plasma discharge is 250W.It addition, make For the purge of gas after plasma discharge, supply 10 seconds purge gas O2And N2.Film-forming temperature now is 90 DEG C.
TiO in cycling condition as above2Film forming speed as described below.I.e., due to unit film forming speed about ForCirculation, after the film forming implementing to circulate 110 times processes the film forming carrying out 10nm thickness, the total ascent time that film forming processes is about It it is 43 minutes.
The moisture-vapor transmission ＞ of ＜ seal coat
Then, the steam for the duplexer with the seal coat (OC layer) realized based on above-mentioned embodiment passes through The experimental result of rate, illustrates several embodiment.Additionally, the experimental result of each embodiment carried out at this is, for above-mentioned reality The gas barrier property of the duplexer that the mode of executing realizes, uses steam permeability determinator (MOCON Aquatran(registered trade mark), Modern Control company (モ ダ ンコ ントロル society) manufactures) to measure steam in the environment of 40 DEG C/90%RH saturating Cross rate and obtain.Fig. 3 is the duplexer to the present embodiment having OC layer and the duplexer of the comparative example being not provided with OC layer is carried out The figure of the comparison of moisture-vapor transmission (WVTR).Thus, the superiority of each embodiment is described while with reference to Fig. 3.
<embodiment 1>
As it is shown on figure 3, in embodiment 1, polyethylene terephthalate (PET) polymer-based of 100 μ m-thick On material, it is formed without UC layer and directly forms the AlO as ALD filmxThin film.Additionally, AlOxThin film (ALD film), is to be set by raw material It is set to TMA(Tri-Methyl Aluminum, trimethyl aluminium), the thickness of 10nm is formed by plasma exposure.
It addition, on the surface of ALD film, form OC layer by organo-mineral complexing coated film.OC layer (organic nothing now Machine composite coating film) raw material, be hydrolysis TEOS(tetraethoxysilane) and PAV(polyvinyl alcohol).Additionally, SiO2And PVA Ratio of components be 70% to 30%.OC layer is to adjust solution that solids content is 5% as smears, 120 DEG C of-1 minute add Bar type rubbing method is used to form 0.5 μm thickness under the conditions of work.
Use the sample of the duplexer of the embodiment 1 formed by so operation, the characteristic of gas barrier property is surveyed Fixed.As a result of which it is, the initial stage measured value of moisture-vapor transmission (WVTR) is 7.5 × 10-3[g/m2/ sky], after caloric test WVTR is 9.8 × 10-3[g/m2/ sky].That is, the duplexer of embodiment 1 is after carrying out caloric test, and WVTR increases about three one-tenth.This Outward, caloric test is cold shock testing (according to JIS C0025), in-30 DEG C (30 minutes)/85 DEG C (30 minutes), 50 circulation Under conditions of carry out.The caloric test of embodiment described later and comparative example is carried out the most under identical condition.
<embodiment 2>
As it is shown on figure 3, in example 2, on the polymer base material of the PET of 100 μ m-thick, carbamate system is used to be coated with Cloth agent and form UC layer.The carbamate system smears of this UC layer, is by commercially available acrylic polyol, HEMA(methyl-prop Olefin(e) acid 2-hydroxyl methyl ester)/MMA(methyl methacrylate) based copolymer, HAMA30mol% molecular weight 10,000, TDI(toluene diisocyanate Acid esters) addition system firming agent is as raw material.Additionally, raw-material ratio of components is NCO/OH=0.5.UC layer is to adjust solid Content be 3% solution as smears, under 120 DEG C of processing conditionss of-1 minute use bar type rubbing method form 0.1 μm film Thick.
Then, AlO is formedxThin film is as the ALD film on UC layer.Additionally, AlOxThin film is that raw material is set as TMA, logical Cross plasma exposure and form the thickness of 10nm.
And then, on the surface of ALD film, form OC layer by organo-mineral complexing coated film.OC layer (organic nothing now Machine composite coating film) raw material be hydrolysis TEOS, silane compound and PAV, SiO2It is 85% to 15% with the ratio of components of PVA. OC layer be adjust solids content be 5% solution as smears, under 120 DEG C of processing conditionss of-1 minute use bar type coating Method forms 0.5 μm thickness.
Use the sample of the duplexer of the embodiment 2 formed by so operation, the characteristic of gas barrier property is surveyed Fixed.As a result of which it is, the initial stage measured value of WVTR is 3.1 × 10-3[g/m2/ sky], the WVTR after caloric test is 6.4 × 10-3[g/ m2/ sky].That is, the duplexer of embodiment 2 WVTR when carrying out caloric test increases to about twice.
<embodiment 3>
As it is shown on figure 3, in embodiment 3, on the polymer base material of the PET of 100 μ m-thick, use containing inorganic substances Carbamate system smears and form UC layer.The carbamate system smears of UC layer, be by commercially available acrylic polyol, HEMA/MMA based copolymer, HAMA30mol% molecular weight 10,000, TDI addition system firming agent and organobentonite are as former material Material.Additionally, raw-material ratio of components is NCO/OH=0.5, inorganic substances are 15wt%.UC layer be adjust solids content be 3% Solution as smears, under 120 DEG C of processing conditionss of-1 minute use bar type rubbing method form 1 μm thickness.
Then, AlO is formedxThin film is as the ALD film on UC layer.Additionally, AlOxThin film (ALD film) is to be set by raw material For TMA, by the thickness of plasma exposure formation 10nm.
It addition, on the surface of ALD film, form OC layer by organo-mineral complexing coated film.OC layer (organic nothing now Machine composite coating film) raw material be hydrolysis TEOS, silane compound, PAV and organic swelling that mean diameter is 0.5 μm Soil, SiO2It is 85% to 15% with the ratio of components of PVA.OC layer be adjust solids content be that the solution of 5% is as smears, 120 Bar type rubbing method is used to form 0.5 μm thickness under the processing conditions of DEG C-1 minute.
Use the sample of the duplexer of the embodiment 3 formed by so operation, the characteristic of gas barrier property is surveyed Fixed.As a result of which it is, the initial stage measured value of WVTR is 0.8 × 10-3[g/m2/ sky], the WVTR after caloric test is 2.1 × 10-3[g/ m2/ sky].That is, the duplexer of embodiment 3 WVTR when carrying out caloric test increases about 2.5 times.
<embodiment 4>
As shown in the embodiment 4 of Fig. 3, in example 4, on the polymer base material of the PET of 100 μ m-thick, use contains The carbamate system smears of inorganic substances and form UC layer.Carbamate system containing the inorganic substances coating of UC layer Agent, is by commercially available acrylic polyol, HEMA/MMA based copolymer, HAMA30mol% molecular weight 10,000, TDI addition system admittedly Agent and TiO2Ultra micron colloidal sol is as raw material.Additionally, raw-material ratio of components is NCO/OH=0.5, inorganic substances are 30wt%.UC layer be adjust solids content be 3% solution as smears, under 120 DEG C of processing conditionss of-1 minute use rod Formula rubbing method forms 0.1 μm thickness.
Then, TiO is formedxThin film is as the ALD film on UC layer.Additionally, TiOxThin film (ALD film) is to be set by raw material For TiCl4, by plasma exposure formed 10nm thickness.
It addition, on the surface of ALD film, form OC layer by organo-mineral complexing coated film.OC layer (organic nothing now Machine composite coating film) raw material be hydrolysis TEOS, silane compound, PAV and mean diameter be the TiO of 20nm2Microgranule, SiO2It is 85% to 15% with the ratio of components of PVA.OC layer be adjust solids content be that the solution of 5% is as smears, at 120 DEG C-1 Minute processing conditions under use bar type rubbing method form 0.5 μm thickness.
Use the sample of the duplexer of the embodiment 4 formed by so operation, the characteristic of gas barrier property is surveyed Fixed.As a result of which it is, the initial stage measured value of WVTR is 1.9 × 10-3[g/m2/ sky], the WVTR after caloric test is 2.1 × 10-3[g/ m2/ sky].That is, the duplexer of embodiment 4 WVTR when carrying out caloric test increases about one one-tenth.
" comparative example "
Then, in order to illustrate the superiority of the moisture-vapor transmission of the duplexer with the present embodiment OC layer, and such as Fig. 3 institute The comparative example shown contrasts.
＜ comparative example 1 ＞
As it is shown on figure 3, in comparative example 1, prepared the stretched film (extending Off ィ Le system) (100 μ m-thick) of PET as high score Subbase material.Further, it is not provided with UC layer at this substrate surface and carries out AlOxThe film forming of film is as ALD film.AlOxThin film is by former material Material is set as TMA, is formed the thickness of 10nm by plasma exposure.Additionally, be not provided with OC layer on the surface of ALD film.
Use the sample of the duplexer of the comparative example 1 formed by so operation, the characteristic of gas barrier property is surveyed Fixed.As a result of which it is, the initial stage measured value of WVTR is 8.5 × 10-3[g/m2/ sky], the WVTR after caloric test is 120.2 × 10-3 [g/m2/ sky].That is, the duplexer of comparative example 1 WVTR after carrying out caloric test increases to more than 14 times.
＜ comparative example 2 ＞
As shown in the comparative example 2 of Fig. 3, comparative example 2 prepares the stretched film (100 μ m-thick) of PET as polymer-based Material.Further, in the PET base material of 100 μ m-thick, carbamate system smears is used to form UC layer similarly to Example 2. The carbamate system smears of UC layer, is commercially available acrylic polyol, HEMA/MMA based copolymer, HAMA30mol% to be divided Son amount 10,000, TDI addition system firming agent are as raw material.Additionally, raw-material ratio of components is NCO/OH=0.5.UC layer is to adjust Solidating body burden is that the solution of 3% is as smears, employing bar type rubbing method formation under 120 DEG C of processing conditionss of-1 minute 0.1 μm thickness.
Then, TiO is formedxThin film is as the ALD film on UC layer.Additionally, TiOxThin film (ALD film) is to be set by raw material For TiCl4, by plasma exposure formed 10nm thickness.It addition, be formed without OC layer on the surface of ALD film.
Use the sample of the duplexer of the comparative example 2 formed by so operation, the characteristic of gas barrier property is surveyed Fixed.As a result of which it is, the initial stage measured value of WVTR is 4.1 × 10-3[g/m2/ sky], the WVTR after caloric test is 80.4 × 10-3 [g/m2/ sky].That is, the duplexer of comparative example 2 WVTR after carrying out caloric test increases about 20 times.
<investigation>
That is, in the vapor barrier properties of the duplexer arranged such as embodiment 1 to embodiment 4 during OC layer, with moisture-vapor transmission (WVTR) initial value is compared, and the value of the WVTR after caloric test does not so increase.On the other hand, such as comparative example 1, compare Vapor barrier properties when being not provided with OC layer of example 2, the value of WVTR after caloric test increases one digit number compared with the initial value of WVTR Above (more than 10 times).For its reason, it is believed that be due to comparative example 1, the duplexer of comparative example 2 sample at ALD film Surface is not provided with OC layer, so producing through hole because of thermal stress etc. at ALD film, thus significantly reduces gas barrier property.The opposing party Face, the sample of the duplexer of embodiment 1 to embodiment 4, is to carry out relative to external stress at the surface configuration OC layer of ALD film Protection, thus do not damage ALD film because of thermal stress etc., therefore the gas barrier property of duplexer does not reduce.
" summary "
As previously discussed, duplexer based on the present invention, by ALD film surface configuration OC formed on polymer base material Layer, will not produce damage to OC layer under the stress caused by environmental change etc., mechanical external force, therefore, it is possible to improve duplexer Gas barrier property.Even it addition, thin ALD film, OC layer also can prevent the damage caused because of external force, therefore, the thickness of thin ALD film It also is able to realize desired properties.
Above, the embodiment of the duplexer of the present invention it is explained in detail with reference to the accompanying drawings, but the concrete structure group of the present invention Become to be not limited to the content of above-mentioned embodiment；Without departing from the spirit and scope of the present invention, even if there being the change in design Deng, they are also both contained in the present invention.It addition, present invention may also apply to the duplexer that realized by foregoing invention with thin slice (film) gas barrier film that shape is formed.
" embodiment of the manufacture method of duplexer "
The manufacture method of the duplexer of embodiment of the present invention, in initial operation, the outer surface along base material is formed thin Membranaceous atomic layer deposition film.Further, in online subsequent processing, contact with rigid bodies such as rollers at atomic layer deposition film Before, seal coat is formed on the surface of this atomic layer deposition film.Specifically, it is common that will be formed with the base of atomic layer deposition film Material is delivered to subsequent processing after being rolled into roll, but in the present embodiment, in order to will be formed with the base material of atomic layer deposition film Be formed as roll, before the direct of travel change roller for changing base material direct of travel contacts with atomic layer deposition film, Seal coat is formed on the surface of atomic layer deposition film.It is expected in the manufacturing process of duplexer, is being formed with ald Before the shape of the base material of film shape in time forming atomic layer deposition film starts to change, formed on the surface of atomic layer deposition film Seal coat.Thus, the scar of the atomic layer deposition film caused because of substrate deformation is prevented, it is possible to keep good gas barrier property.
Here, needing seal coat is the film higher than the mechanical strength of atomic layer deposition film.Or, have in seal coat In the case of the mechanical strength identical with atomic layer deposition film, then needing seal coat is to be thicker than the thickness of atomic layer deposition film The layer formed.It reason for this is that, even if atomic layer deposition film produces scar under external force and produces through on film thickness direction Hole, seal coat also will not produce through hole under the external force of this degree on film thickness direction, therefore, it is possible to retaining layer well The gas barrier property of stack.Additionally, between base material and atomic layer deposition film, both could be formed with priming coat, it is also possible to be formed without Priming coat.
The manufacture method of the duplexer of embodiment of the present invention, it is possible to use following laminated body producing device to realize, its In, this laminated body producing device has the online covering coated body forming ALD film 4 and OC layer 5 at online series connection in-process Forming portion.Now, for the manufacture method of the duplexer of present embodiment, even as shown in Figure 1 be formed without UC layer Duplexer 1a, the duplexer 1b being formed with UC layer 3 as shown in Figure 2, also can use.That is, can either with or without UC layer Relative to the base material of rolled (film (film) shape) when being enough applied to formation ALD film 4 and OC layer (protection coated body) 5 in online Make in volume to volume mode in the manufacturing process of duplexer 1a, 1b that the thin film of ALD film 4 carries out depositing.
Generally, the ALD film 4 being formed (deposition) on base material 2 is fine and close thin film, even very thin thickness is (such as 10nm) it also is able to play excellent gas barrier property.But, owing to the thickness of ALD film 4 is thin, therefore, using ALD with volume When volume mode is carried out deposition (film forming) of thin film, duplexer 1(1a, the 1b after carrying out film forming at ALD film 4) for, logical Cross contacting between the guide roller with induction system etc., the base material contact etc. each other when winding, it is possible to can be at ALD film Scar, pin hole etc. is produced on 4.If producing scar, pin hole by so operation at ALD film 4, then can cause the choke of duplexer 1 Performance reduces.
The tiny flaw produced on ALD film 4, (such as steams at water in the case of gas barrier property is required low duplexer 1 Vapor permeability (WVTR) is 1.0g/m2In the case of/sky), problem in practical use can't be become.But, if WVTR is 1 × 10-3g/m2Below/sky, then in the case of needing the duplexer 1 of high-gas resistance, problem can occur in air-tightness.
Such as, before and after the duplexer 1 after film forming ALD film 4 carries out contacting (winding) with guide roller, use optical microscope Observe the surface of ALD film 4, then before making duplexer 1 contact guide roller, on ALD film 4, there is no scar, but make duplexer 1 connect After touching guide roller, ALD film 4 produces many scars.For this scar, by with H2SO4(sulphuric acid) processes ALD film 4 Surface and make the base material 2(under scar such as, PET: polyethylene terephthalate) dissolve, therefore, it is possible to easily enter Row is observed.That is, when the duplexer 1 after film forming ALD film 4 is once wound through guide roller, it is possible to make WVTR increase by 1 ×10-3g/m2More than/sky.
Therefore, in order to prevent due to contacting between guide roller with duplexer 1, duplexer 1 when winding layer stack 1 that The caused scar of ALD film 4 such as the contact between this, pin hole (through hole), in online after just film forming ALD film 4, Before duplexer 1 contacts guide roller, the film forming carrying out the seal coat (OC layer) 5 as protection coated body processes.
The material of OC layer 5 now, preferably organic polymer, acrylate monomer, propylene can be enumerated as an example Acid monomers and the mixture etc. of acrylate oligomer.Additionally, it is preferred that the thickness of OC layer 5 becoming protection coated body be 1 μm with On.Additionally, carried out the method protecting the film forming of coated body by OC layer 5 on the surface of ALD film 4, it is the most direct with mechanical part The method on contact ALD film 4 surface is carried out.
By the film-forming process of the protection coated body that OC layer 5 is carried out, it is that the film forming with ALD film 4 is implemented, therefore in online Both coating speeds must be identical with the proper range of vacuum.It addition, when carrying out protection coating according to OC layer 5, due to The coated face of contact ALD film 4 can become generation pin hole, the reason of scar, so the most preferably contacting the coated face of ALD film 4, and excellent Choosing can complete the method for the protection coating of OC layer 5 in a non contact fashion.
It addition, when carrying out the film forming of ALD film 4 under vacuo, in order to keep required vacuum, implement protection coating OC layer The technique of 5 can not produce gas in a large number.From the above point of view, according to the film-forming process of the protection coating of OC layer 5, it is suitable for vacuum Technique, noncontact and in smears without the flash distillation vapour deposition method of solvent (i.e., the generation of escaping gas is few).
<the 3rd embodiment: form OC layer by flash distillation vapour deposition method>
In the third embodiment, illustrate to be formed the manufacture method of the duplexer of OC layer by flash distillation vapour deposition method.Flash distillation is steamed Plating method is method monomer, oligomer etc. being coated with desired thickness in a vacuum, it is possible to do not produce A large amount of volatile ingredients of solvent etc. and made acrylate layer be deposited on base material by low heat loads in a vacuum.Now, it is possible to Using is liquid and the most solvent-laden acrylic monomers, acrylic acid oligomer etc. at normal temperatures.
Fig. 4 is the laminated body producing device being formed OC layer by flash distillation vapour deposition method being applied to third embodiment of the invention The summary construction diagram of 10a.This laminated body producing device 10a includes implementing the ALD film forming mechanism 11 of the film forming of ALD film 4, being arranged at The downstream of ALD film forming mechanism 11 and OC layer 5 is formed at the covering coated body forming portion 21 on ALD film 4 surface, cylinder 13 and Various rollers (release roller 14a, take-up roll 18b etc.).
The structural element comprising ALD film forming mechanism 11 and cylinder 13 and various roller is constituted as follows.That is, include as Lower structure and constitute: cylinder (supporting mass) 13, to being formed as thin plate, thin slice (film, film) or the long substrate 12 of membranaceous banding A face of thickness direction support；Conveying mechanism 14, by along cylinder 13 by putting that base material 12 carries in one direction Go out roller 14a and pony roll 14b to be constituted；Plasma pretreatment portion 16, carries out plasma pretreatment to base material 12；ALD film forming Portion 17a, 17b, 17c, by make to insert between itself and the surface of cylinder 13 carry out in the way of base material 12 configuring and by ALD film before Drive on another face of the thickness direction that body is attached to base material 12；Winding mechanism 18, is arranged on the conveying direction of base material 12 Cover the downstream of coated body forming portion 21 and by will be formed with the base material volume 12 of ALD film 4 and OC layer 5 in roll mode Around regulation roller 18a and take-up roll 18b constitute.
The regulation roller 18a of winding mechanism 18 has the applying regulation tension force when being wound in take-up roll 18b by base material 12 Function.It addition, figure 4 illustrates three ALD film forming portions 17a, 17b, 17c, but need actually to arrange and be capable of The film forming of the ALD of ALD film 4 required film thickness circulates corresponding number.Such as, if when setting the thickness that ALD film 4 is 10nm The film forming circulation needing ALD is 70 circulations, then need to arrange 70 ALD film forming portions.Additionally, release roller 14a, cylinder 13 and volume Direction of rotation around roller 18b is the direction of arrow (counterclockwise) of Fig. 4.
It addition, the covering coated body forming portion 21 forming (coating) OC layer 5 on the surface of ALD film 4 includes following structure: former Material container 22, raw material pipe arrangement 23, feedstock transportation pump 24, nebulizer (aerosol apparatus) 25, gasifier (vaporizer) 26, gas pipe arrangement 27, coating nozzles 28, and in order to cross-link, solidify the OC layer 5(acrylate layer that ALD film 4 surface is coated with) and irradiate electronics and penetrate Line, UV(ultraviolet) irradiation portion 29.
Additionally, cylinder (supporting mass) 13 supports this base material 12 so that base material 12 is at ALD film forming portion 17a, 17b, 17c And keep definite shape between winding mechanism 18.Based on this, at the uniformly coating OC layer 5 of ALD film 4.
Then, illustrate to use the laminated body producing device 10a shown in Fig. 4 to be deposited with the behaviour that forms OC layer 5 by flash distillation Make.First, in ALD film forming mechanism 11, use common ALD by ALD film 4 film forming on base material 2.Here, explanation uses High molecular base material 2 is carried out with aluminium oxide (Al by takeup type ALD2O3) film forming of the thin film of ALD film 4 that constitutes.
First, in step 1, the poly terephthalic acid of 100 μ m-thick as the high molecular base material of film (film) shape 2 it is wound around The stretched film of glycol ester (PET), and the releasing roller 14a of the conveying mechanism 14 being installed in laminated body producing device 10.
Further, in step 2, the film sent successively from the pony roll 14b of the unreeling shaft as conveying mechanism 14 (film) shape base material 12, supports the back side by cylinder (supporting mass) 13, while utilizing plasma pretreatment portion 16 to lead to Cross to be exposed in oxygen plasma environment and implement surface modification.The condition of plasma exposure now is according to base material 12 Detailed characteristics and suitably select.
Then, in step 3, base material 12 is after plasma exposure terminates, to the environment being in noble gas (nitrogen) In cleaning area 17a1 of ALD film forming portion 17a of ALD film forming mechanism 11 move.
Then, in step 4, base material 12 enters the scope of ALD film forming portion 17a, after cleaning area 17a1, first The environment of presoma region 17a2 adsorbs trimethyl aluminium.This first presoma region 17a2, is in nitrogen and trimethyl aluminium Environment, is held in pressure about 10～50Pa, inner wall temperature about 70 DEG C.
Then, in steps of 5, cleaning area 17a1 of next section shifted to by base material 12, removes excess in its environment First presoma.
And then, in step 6, base material 12 shifts to the second presoma region 17a3 from cleaning area 17a1.This second forerunner Body region 17a3, is in the environment of nitrogen and water, is held in pressure about 10～50Pa, inner wall temperature about 70 DEG C.This second In the 17a3 of presoma region, water and the trimethyl aluminium being adsorbed in base material 12 react.
Then, in step 7, in the base material 12 dividing plate between the second presoma region 17a3 and cleaning area 17a1 Set gap (not shown) and be transported to next cleaning area 17a1, remove the of excess in this cleaning area 17a1 Two presomas.
Process as 1 circulation using the film forming of ALD film 4 using above-mentioned steps 1 to step 7 to be implemented, at the table of base material 12 Face is formed with the ALD film 4 of the duplexer of 1 layer of part.Figure 4 illustrates and use the 3 of 3 ALD film forming portion 17a, 17b, 17c compositions Circulation, but in practical operation can by 70 ALD film forming portions 17 implement the film forming of 70 circulations process, shape on base material 12 surface Become the aluminium oxide (Al of the about 10nm as ALD film 42O3) thin film.
In ALD film forming portion, 17a, 17b, 17c are formed based on aluminium oxide (Al2O3) thin film and the base material of ALD film 4 that obtains 12, it is transported to cover coated body forming portion 21, forms the OC layer 5 as protection coated body covering coated body forming portion 21.
In the flash distillation evaporation covered in coated body forming portion 21, by feedstock transportation pump 24 from material container 22 send in The painting cloth material (acrylic monomers etc.) of raw material pipe arrangement 23, is to be dripped by nebulizer (aerosol apparatus) 25.Further, by nebulizer The painting cloth material (acrylic monomers etc.) that (aerosol apparatus) 25 is dripped, becomes while the wall of contact gasifier (vaporizer) 26 Become gas shape.
Further, in gasifier 26, become the painting cloth material of gas shape (gaseous state), join via the gas being held under high temperature Pipe 27, spreads to coating nozzles 28.And then, from coating nozzles 28, it is coated with cloth material coagulation in base with spray form effluent air shape The surface of material 12.Then, the OC layer 5 that the painting cloth material in the surface coagulation of base material 12 is formed, is being shone from irradiation portion 29 Crosslink under the electron ray penetrated, UV light, solidify.Additionally, the coating section of OC layer 5 (covering coated body forming portion 21) is logical Often remain the environment of the non-active gas such as nitrogen so that the crosslinking being coated with cloth material is not suppressed.
It addition, the amount being coated with cloth material dripped by gasifier 26 by the regulation unit interval, it is possible to arbitrarily regulation OC layer 5 The thickness of coating.Such as, when hope thickeies the coating film thickness of OC layer 5, increase dripping of the painting cloth material for gasifier 26 Dosage, when wishing the coating film thickness of thinning OC layer 5, then reduces the dripping quantity being coated with cloth material for gasifier 26.By such as This operation, the uniformity of the coating film thickness of OC layer 5 can be carried out by keeping the droplets of material dosage of the time per unit fixed Control.
That is, in ALD film forming mechanism 11, it is formed based on aluminium oxide (Al2O3) and the base material of the thin film of ALD film 4 that obtains 12, in the way of the most not contact mechanism parts etc., the covering coated body being delivered to be formed protection coated body (OC layer 5) is formed Portion 21.On the other hand, in covering coated body forming portion 21, acrylic acid coated dose is released from coating nozzles 28 in steam mode (such as, acrylic monomers, oligomer, light trigger etc.).Therefore, have based on aluminium oxide (Al in film forming2O3) and the ALD that obtains The base material 12 of film 4, can be at aluminium oxide (Al when coating nozzles 282O3) on film surface coagulation have based on acrylic acid coated dose And the OC layer 5 obtained.
Then, at aluminium oxide (Al2O3) the surface deposition of thin film (ALD film 4) have the base of OC layer 5 of acrylic acid coated dose Material film (base material Off ィ Le system) (duplexer 1), (the irradiation portion, irradiated region of the UV lamp being transported in irradiation portion 29 or electron ray 29).Here, when base material film (duplexer 1) is by the irradiation portion 29 of irradiation UV light or electron ray, make acrylic acid coated dose It is solidified to form the OC layer 5 of about 1 μm.
By so operation, the base material film (duplexer 1) being formed with OC layer 5 based on flash distillation evaporation is delivered to up-coiler Structure 18, applies certain tension force, while being wound in take-up roll 18b by regulation roller 18a.So that aluminium oxide (Al2O3) Thin film (ALD film 4) becomes directly not regulate roller 18a, take-up roll 18b with winding mechanism 18() contact.It addition, by base material film After (duplexer 1) is wound in take-up roll 18b, there is no aluminium oxide (Al yet2O3) thin film (ALD film 4) carries out the Gu that contacts directly with one another Consider.As a result of which it is, do not produce pin hole, the Gu of scar on the ALD film 4 of base material film (duplexer 1) being wound in take-up roll 18b Consider, therefore, it is possible to produce the duplexer 1 of high-quality under reeling condition.
<the 4th embodiment: form OC layer by CVD>
In the 4th embodiment, illustrate to be formed the manufacturer of the duplexer of OC layer by CVD, i.e. chemical vapour deposition technique Method.Fig. 5 is the outline of the laminated body producing device 10b being formed OC layer by CVD being applied to four embodiment of the invention Structure chart.For including the structure of ALD film 4 film forming ALD film forming mechanism 11, cylinder 13 and various roller on base material 12, Due to identical with Fig. 4, so omitting the explanation to these structures.
Cover coated body forming portion 31 and include that following structure is constituted: supply the plasma high frequency of such as 13.56MHz The RF(radio frequency (Radio Frequency) of electricity: high frequency) power supply 32；The frequency of plasma high-frequency electrical is carried out The adapter (matching box) 33 joined；Plasma discharge electrode 34 for chemical gaseous phase deposition；Ozone supply, O2 Gas container 35 Deng gas；Measure ozone, O2Environmental gas effusion meter 36 Deng the quantity delivered of environmental gas；Supply CVD uses HMDSO(Hexamethyldisiloxane: hexamethyl disiloxane) etc. the material container 37 of fluorocarbon gas；With And, measure the raw material gas flow gauge 38 of the quantity delivered of the fluorocarbon gas of HMDSO etc..
Then, illustrate to use the laminated body producing device 10b shown in Fig. 5 and formed the operation of OC layer 5 by CVD.First First, according to described in aforementioned 3rd embodiment when carrying out flash distillation evaporation as method, adopt in ALD film forming mechanism 11 With common ALD by by Al thick for 10nm2O3ALD film 4 film forming that film is constituted is in the surface of polymer base material 12.
Utilize ALD film forming portion 17a, 17b, 17c and film forming has Al2O3The base material 12 of thin film (ALD film 4), implement with the 3rd Situation described in mode is similarly shifted to cover coated body forming portion 31.Then, there is Al in film forming2O3The base material 12 of thin film passes through When covering coated body forming portion 31, common CVD is used to form SiO with the thickness of 1 μm2Thin film.
Now, in covering coated body forming portion 31, from RF power supply 32, the electrode 34 of CVD is applied frequency 13.56MHz High-frequency electrical 1.0kW.It addition, supply into, from material container 37, the hexamethyl disiloxane (HMDSO) that film pressure is 10Pa.Will now HMDSO import volume be set to 100sccm.It addition, the ozone gas import volume from gas container 35 is set to 100sccm.Separately On the one hand, the electrode spacing in the electrode 34 of CVD is set to 30mm.It addition, base material 12 to be set to the poly terephthalic acid of 100 μ m-thick Glycol ester (PET).
By so operation, the base material film (duplexer 1) being formed with OC layer 5 based on CVD is delivered to winding mechanism 18, one While apply certain tension force by regulation roller 18a, it is wound in take-up roll 18b.So that Al2O3Thin film (ALD film 4) Become directly not regulate roller 18a, take-up roll 18b with winding mechanism 18() contact.It addition, base material film (duplexer 1) is being wound After take-up roll 18b, there is no Al yet2O3Thin film (ALD film 4) carries out the misgivings contacted directly with one another.As a result of which it is, not at volume Pin hole, the misgivings of scar are produced on the ALD film 4 of the base material film (duplexer 1) being around in take-up roll 18b, therefore, it is possible at rolled The duplexer 1 of high-quality is produced under state.
The manufacturing process ＞ of ＜ duplexer
Based on above said content, illustrate to use laminated body producing device 10a, the 10b shown in Fig. 4 or Fig. 5 to implement The manufacturing process of duplexer 1.Fig. 6 is to carry out the manufacturing process of duplexer when being not provided with UC layer in embodiment of the present invention The flow chart summarized.It addition, Fig. 7 is to carry out the manufacturing process of duplexer when being provided with UC layer in embodiment of the present invention The flow chart summarized.
Initially explanation uses the manufacturing process of duplexer 1a when being not provided with UC layer of Fig. 6.First, along polymer base material ALD film 4(step S1 of the outer surface forming film shape of 2).Secondly, it is being in the in-process that the formation with ALD film 4 carries out connecting Online in, the outer surface along ALD film 4 forms the mechanical strength OC layer 5 high than this ALD film 4 thus generation layer stack 1a(walks Rapid S2).In addition, it is possible in step s 2, along the outer surface of ALD film 4, there is the mechanical strength identical with this ALD film 4 also And the film of this ALD film 4 thickness of Film Thickness Ratio forms OC layer 5, thus generation layer stack.Then, OC layer 5 is contacted with take-up roll 18b And being collected in winding manner duplexer 1a(step S3).
Thus, make OC layer 5 contact regulation roller 18a, take-up roll 18b that mechanical strength is higher than ALD film 4, and make ALD film 4 not Directly contact regulation roller 18a, take-up roll 18b, therefore, will not make ALD film 4 produce scar.As a result of which it is, can the most well The gas barrier property of retaining layer stack 1a, while this duplexer 1a is wound in take-up roll 18b.Even if it addition, OC layer 5 have with The mechanical strength that ALD film 4 is identical, if the thickness of the Film Thickness Ratio ALD film 4 of OC layer 5, even if then applying somewhat ALD film 4 to be produced scar The external force of degree, does not also produce the misgivings of through hole at OC layer 5.Its result is can the choke of retaining layer stack 1a well Property.
Secondly, the manufacturing process of duplexer 1b when being provided with UC layer of use Fig. 7 be described.First, along polymer-based The outer surface of material 2, forms UC layer 3(step S11 containing at least one in inorganic substances or organic polymer).Then, with The mode that at least one in the inorganic substances exposed with UC layer 3 surface or organic polymer is combined, on UC layer 3 surface Form film like ALD film 4(step S12).And then, be in the in-process that carries out with the formation of ALD film 4 connecting online in, Outer surface along ALD film 4 forms the mechanical strength OC layer 5 higher than this ALD film 4 thus generation layer stack 1b(step S13).This Outward, it is possible in step s3, along the outer surface of ALD film 4, to have the mechanical strength identical with this ALD film 4 and Film Thickness Ratio The film of this ALD film 4 thickness forms OC layer 5, thus generation layer stack 1b.Then, OC layer 5 is contacted with take-up roll 18b and wind Accommodation layer stack 1b(step S14).
Thus, make OC layer 5 contact regulation roller 18a, take-up roll 18b that mechanical strength is higher than ALD film 4, and make ALD film 4 not Directly contact regulation roller 18a, take-up roll 18b, produce scar thus without making ALD film 4.Its result is can retaining layer well The gas barrier property of stack 1b.It addition, even if OC layer 5 has the mechanical strength identical with ALD film 4, if the Film Thickness Ratio ALD film 4 of OC layer 5 Thickness, even if then applying somewhat to make ALD film 4 produce the external force of scar degree, also do not produce the misgivings of through hole at OC layer 5. Its result is can the gas barrier property of retaining layer stack 1b well.
" embodiment "
<embodiment 1>
In embodiment 1, the laminated body producing device 10a of Fig. 4 is used to be deposited with by flash distillation and form OC layer.That is, such as Fig. 8 Shown in, in embodiment 1, using the poly-terephthaldehyde of 100 μ m-thick through winding the film (film) as polymer base material The stretched film of acid glycol ester (PET), is installed on the releasing roller 14a of laminated body producing device 10a.Then, will be from pony roll 14b The film (film) (base material 12) sent successively, by plasma exposure portion 16, at 300W, is exposed to O under conditions of 180 seconds2 The environment of plasma is implemented surface modification.And then, after plasma exposure, above-mentioned film (film) is moved by cylinder 13 To N2The ALD film forming forming portion 11 of gaseous environment.
Then, above-mentioned film (film) is imported ALD film forming portion 17a, and through as O2Gas and N2The mixed gas of gas After cleaning area 17a1 of environment, as keeping inner wall temperature to be about the 10 of 70 DEG C～the N of 50Pa2Gas and trimethyl aluminium (TMA), in the first presoma region 17a2 of environment, TMA is adsorbed in the surface of above-mentioned film (film).
And then, above-mentioned film (film) is shifted to next cleaning area 17a1, removes the first presoma of excess there. Then, above-mentioned film (film) is shifted to the second presoma region 17a3 from cleaning area 17a1, be about 70 keeping inner wall temperature DEG C 10～50Pa N2Gas and H2In second presoma region 17a3 of the mixed-gas environment of O gas, by H2O is adsorbed in On film (film).Now, H2O and TMA reaction and at the Surface Creation aluminium oxide (Al of above-mentioned film (film)2O3).
Then, institute in the above-mentioned film (film) dividing plate between the second presoma region 17a3 and cleaning area 17a1 is made The gap arranged, is delivered to next cleaning area 17a1, removes the second presoma of excess in this cleaning area 17a1.
To operate as described above and be set to 1 circulation, such as ALD film forming portion 17a → ALD film forming portion 17b → ALD film forming portion 17c ... the film forming so implementing 70 circulations processes, and result is the aluminium oxide (Al of about 10nm2O3) thin film (barrier layer) is formed at The surface of film (film).
Then, employing ALD film forming mechanism 11 is formed with aluminium oxide (Al2O3) the film of thin film be delivered to cover coated body Forming portion 21.In covering coated body forming portion 21, at the aluminium oxide (Al on film (film) surface2O3On), stacking is by 2-hydroxyl 90/10(weight % of base-3-phenoxypropylacrylate and ethoxylated neopentylglycol diacrylate) mixture institute structure The thickness become is the uncured coating layer obtained based on flash distillation evaporation of 1 μm.
Then, irradiate electron ray from irradiation portion 29 to the coating layer obtained based on flash distillation evaporation, make coating layer solidify, Form the acrylic acid coated layer (acrylic resin) that thickness is 1 μm as seal coat (OC layer).Then, will be based on flash distillation Evaporation and be formed with the film (film) of OC layer and be delivered to winding mechanism 18, by the regulation roller 18a film to being formed with OC layer (film) apply certain tension force, above-mentioned film (film) is rolled in take-up roll 18b.
Use the sample of the film (film) (duplexer) of the embodiment 1 formed by so operation, the spy to gas barrier property Property is determined.As a result of which it is, the measured value of moisture-vapor transmission (WVTR) is 1.5 × 10-3[g/m2/ sky].
<embodiment 2>
In example 2, the laminated body producing device 10b of Fig. 5 is used to be formed OC layer by CVD.I.e., as shown in Figure 8, In example 2, use and the identical method of embodiment 1, in ALD film forming mechanism 11 by the aluminium oxide (Al of about 5nm2O3) Thin film (barrier layer) is formed in the stretched film of polyethylene terephthalate (PET) of 100 μ m-thick.
Then, employing ALD film forming portion mechanism 11 is defined aluminium oxide (Al2O3) the film (film) of thin film be delivered to cover Lid coated body forming portion 31.In covering coated body forming portion 31, by hexamethyl disiloxane (HMDSO) 100sccm and ozone The mixed gas of 100sccm imports between the electrode 34 of CVD, applies the frequency from RF power supply 32 between electrode 34 High-frequency electrical 1.0kW of 13.56MHz, thus carry out plasmarized.Further, at the aluminium oxide on above-mentioned film (film) surface (Al2O3On), form the silicon oxide film (SiO of about 1 μm as OC layer2Film).
Then, the film (film) being formed with OC layer based on CVD is delivered to winding mechanism 18, by 18a pair, roller of regulation The film (film) being formed with OC layer applies certain tension force, rolls above-mentioned film (film) in take-up roll 18b.
Use the sample of the duplexer of the embodiment 2 formed by so operation, the characteristic of gas barrier property is surveyed Fixed.As a result of which it is, the measured value of moisture-vapor transmission (WVTR) is 2.2 × 10-3[g/m2/ sky].
" comparative example "
Then, in order to illustrate the superiority of the moisture-vapor transmission of the duplexer with the present embodiment OC layer, and such as Fig. 8 institute The comparative example shown contrasts.
＜ comparative example 1 ＞
As shown in Figure 8, in comparative example 1, use and the identical method of embodiment 1, will about in ALD film forming mechanism 11 Aluminium oxide (the Al of 5nm2O3) thin film (barrier layer) is formed at the stretching of the polyethylene terephthalate (PET) of 100 μ m thick On film.Then, when not forming OC layer, above-mentioned film (film) is delivered to winding mechanism 18.Then, by regulation roller 18a applies certain tension force to the film (film) not forming OC layer, rolls above-mentioned film (film) in take-up roll 18b.
Use the sample of the duplexer of the comparative example 1 formed by so operation, the characteristic of gas barrier property is surveyed Fixed.As a result of which it is, the measured value of moisture-vapor transmission (WVTR) is 3.0 × 10-2[g/m2/ sky].That is, winding mechanism 18 is being used When winding is not provided with film (film) (duplexer) of OC layer as comparative example 1, use volume shown in embodiment 1, embodiment 2 Comparing when mechanism 18 winding is provided with film (film) (duplexer) of OC layer, WVTR reduces about one digit number.In other words, if adopting Be not provided with the film (film) (duplexer) of OC layer with winding mechanism 18 winding, then gas barrier property significantly deteriorates.
" summary "
As previously discussed, the ALD film surface configuration OC layer formed on polymer base material based on the present invention, thus right at volume Scar, pin hole will not be produced on OC layer under mechanical external force (stress) effect produced by the laminated body producing device of volume mode, Therefore, it is possible to improve the gas barrier property of duplexer.As a result of which it is, can be coated with by the ALD film of winding method high-speed production high-quality Film (film).
Above, the embodiment of the duplexer of the present invention it is explained in detail with reference to the accompanying drawings, but the concrete structure group of the present invention Become to be not limited to the content of above-mentioned embodiment；Without departing from the spirit and scope of the present invention, even if there being the change in design Deng, they are also both contained in the present invention.It addition, set forth manufacture method and the duplexer of duplexer in the above-described embodiment Manufacture device, but be not limited thereto.Accommodating doubtful, it is also possible to be applied to be formed as the duplexer realized according to the present invention The manufacture method of the gas barrier film of film (film) shape, manufacture device.
Industrial applicibility
The duplexer of the present invention, it can be applied to electroluminescent cell (EL element), liquid crystal display, semiconductor wafer Deng electronic unit be self-evident, it can also be effectively applied to packaging film (the packaging Off ィ of pharmaceuticals or food etc. Le system), the packaging film etc. of precise part.
It addition, the present invention can also be efficiently applied to, manufacture electroluminescent cell (EL element), liquid crystal display, partly lead The semiconductor-fabricating device of the semiconductor devices such as body wafer, and manufacture the bag of the packaging film of pharmaceuticals, food, precise part etc. Dress film manufacturing device etc..
The explanation of reference
1a, 1b duplexer
2,12 base material
3 priming coats (UC layer)
4 atomic layer deposition films (ALD film)
5 seal coats (OC layer)
10a, 10b laminated body producing device
11 ALD film forming mechanisms
13 cylinders (supporting mass)
14 conveying mechanisms
14a releases roller
14b pony roll
16 plasma pretreatment portions
17a, 17b, 17c ALD film forming portion
17a1 cleaning area
17a2 the first presoma region
17a3 the second presoma region
18 winding mechanisms
18a regulates roller
18b take-up roll
21,31 coated body forming portion is covered
22 material containers
23 raw material pipe arrangements
24 feedstock transportation pumps
25 nebulizers
26 gasifiers
27 gas pipe arrangements
28 coating nozzles
29 irradiation portions
32 RF power supplys
33 adapters
34 electrodes
35 gas containers
36 environmental gas effusion meters
37 material containers
38 raw material gas flow gauge

Claims (12)

1. a duplexer, it is characterised in that comprising:
Base material；
The atomic layer deposition film formed along the outer surface of described base material；And,
The seal coat of this atomic layer deposition film is covered with the film that mechanical strength is higher than described atomic layer deposition film,
Further, described seal coat is to stop that coated body is formed by water system, and described water system stops that coated body is to pass through water system Organic polymer, containing metal alkoxide or silane coupler organo-metallic compound composition hydrating polymer and they Complex constitute,
Further, described water system stop coated body have in OH base and COOH base at least any one, and there is block.
2. a duplexer, it is characterised in that comprising:
Base material；
The atomic layer deposition film formed along the outer surface of described base material；And,
To have the film of ald thickness described in the mechanical strength identical with described atomic layer deposition film and Film Thickness Ratio Cover the seal coat of this atomic layer deposition film,
Further, described seal coat is to stop that coated body is formed by water system, and described water system stops that coated body is to pass through water system Organic polymer, containing metal alkoxide or silane coupler organo-metallic compound composition hydrating polymer and they Complex constitute,
Further, described water system stop coated body have in OH base and COOH base at least any one, and there is block.
3. duplexer as claimed in claim 1 or 2, it is characterised in that described seal coat contains inorganic substances.
4. duplexer as claimed in claim 1 or 2, it is characterised in that between described base material and described atomic layer deposition film, Also have: be dispersed with the priming coat of the inorganic substances being combined with described atomic layer deposition film, or contain and described atom The organic macromolecule priming coat that layer deposition film is combined.
5. a gas barrier film, it is characterised in that it has the duplexer described in claim 1 or 2, and by the described stacking bodily form Become membranaceous.
6. the manufacture method of a duplexer, it is characterised in that comprising:
First operation, this operation is along the atomic layer deposition film of the outer surface forming film shape of base material；
Second operation, this operation be in the in-process connected with described first operation online in, along described atomic layer deposition The outer surface of integrated membrane, forms the seal coat that mechanical strength is higher than this atomic layer deposition film, generation layer stack；And,
3rd operation, in the way of the seal coat that this operation is formed in described second operation contacts with rigid body, receives institute State duplexer,
Further, described seal coat is to stop that coated body is formed by water system, and described water system stops that coated body is to pass through water system Organic polymer, containing metal alkoxide or silane coupler organo-metallic compound composition hydrating polymer and they Complex constitute,
Further, described water system stop coated body have in OH base and COOH base at least any one, and there is block.
7. the manufacture method of a duplexer, it is characterised in that comprising:
First operation, this operation is along the atomic layer deposition film of the outer surface forming film shape of base material；
Second operation, this operation be in the in-process connected with described first operation online in, along described atomic layer deposition The outer surface of integrated membrane, to have the mechanical strength identical with described atomic layer deposition film and this ald thickness of Film Thickness Ratio Film form seal coat, generation layer stack；And,
3rd operation, in the way of the seal coat that this operation is formed in described second operation contacts with rigid body, receives institute State duplexer,
Further, described seal coat is to stop that coated body is formed by water system, and described water system stops that coated body is to pass through water system Organic polymer, containing metal alkoxide or silane coupler organo-metallic compound composition hydrating polymer and they Complex constitute,
Further, described water system stop coated body have in OH base and COOH base at least any one, and there is block.
8. the manufacture method of a duplexer, it is characterised in that comprising:
First operation, this operation, along the outer surface of base material, is formed containing at least one in inorganic substances and organic polymer Priming coat；
Second operation, this operation with the inorganic substances that expose on the surface of the priming coat formed in described first operation and having The mode that at least one in machine macromolecule is combined, at the ald of the outer surface forming film shape of described priming coat Film；
3rd operation, this operation be in the in-process connected with described second operation online in, along described atomic layer deposition The outer surface of integrated membrane, forms the seal coat that mechanical strength is higher than this atomic layer deposition film, generation layer stack；And,
4th operation, in the way of the seal coat that this operation is formed in described 3rd operation contacts with rigid body, receives institute State duplexer,
Further, described seal coat is to stop that coated body is formed by water system, and described water system stops that coated body is to pass through water system Organic polymer, containing metal alkoxide or silane coupler organo-metallic compound composition hydrating polymer and they Complex constitute,
Further, described water system stop coated body have in OH base and COOH base at least any one, and there is block.
9. the manufacture method of a duplexer, it is characterised in that comprising:
First operation, this operation, along the outer surface of base material, is formed containing at least one in inorganic substances and organic polymer Priming coat；
Second operation, this operation with the inorganic substances that expose on the surface of the priming coat formed in described first operation and having The mode that at least one in machine macromolecule is combined, at the ald of the outer surface forming film shape of described priming coat Film；
3rd operation, this operation be in the in-process connected with described second operation online in, along described atomic layer deposition The outer surface of integrated membrane, to have the mechanical strength identical with described atomic layer deposition film and this ald thickness of Film Thickness Ratio Film form seal coat, generation layer stack；And,
4th operation, in the way of the seal coat that this operation is formed in described 3rd operation contacts with rigid body, receives institute State duplexer,
Further, described seal coat is to stop that coated body is formed by water system, and described water system stops that coated body is to pass through water system Organic polymer, containing metal alkoxide or silane coupler organo-metallic compound composition hydrating polymer and they Complex constitute,
Further, described water system stop coated body have in OH base and COOH base at least any one, and there is block.
10. the manufacture method of the duplexer as according to any one of claim 6 to 9, it is characterised in that
Described rigid body is take-up roll, after described 3rd operation or described 3rd operation, by described duplexer in roll mode Carry out contacting with described take-up roll thus wind, receive this duplexer.
11. 1 kinds of laminated body producing devices, it will have atomic layer being formed as film forming on thin plate, thin slice or membranaceous banding substrate The duplexer of deposition film, at online in-process, carries in volume to volume mode, it is characterised in that comprising:
Supporting mass, this supporting mass supports in a thickness direction face of described base material；
Conveying mechanism, described base material is carried in one direction by this conveying mechanism along the outer surface of described supporting mass；
Ald film forming portion, this ald film forming portion is so that described base material inserts this ald film forming portion and institute The mode stated between the outer surface of supporting mass configures, and make described atomic layer deposition film film forming in this base material at thickness direction On another face；
Cover coated body forming portion, the described atomic layer that this covering coated body forming portion is arranged on the conveying direction of described base material Deposition film forming portion downstream, the surface of described atomic layer deposition film formed mechanical strength stronger than described atomic layer deposition film, Or the seal coat of this ald thickness of Film Thickness Ratio；And,
Winding mechanism, under the described covering coated body forming portion that this winding mechanism is arranged on the conveying direction of described base material Trip, is wound into roll as contact surface by described duplexer using described seal coat,
Further, described seal coat be by water system stop coated body formed, described water system stop coated body have OH base and In COOH base at least any one.
12. laminated body producing devices as claimed in claim 11, it is characterised in that
What it was additionally included on the conveying direction of described base material is configured at the primary coat formation of upstream, described ald film forming portion Portion,
Further, described primary coat forming portion, formed to have at described substrate outer surface and be combined with described atomic layer deposition film The priming coat of binding site.
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Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103732392B (en) * 2011-07-28 2015-11-25 凸版印刷株式会社 Duplexer, gas barrier film and their manufacture method
CN103732393B (en) * 2011-07-28 2016-10-05 凸版印刷株式会社 Duplexer, gas barrier film, the manufacture method of duplexer and laminated body producing device
KR102197243B1 (en) * 2013-03-27 2021-01-04 도판 인사츠 가부시키가이샤 Laminate and gas barrier film
EP2979857B1 (en) * 2013-03-27 2024-03-20 Toppan Printing Co., Ltd. Laminate body, barrier film, and manufacturing method of these
TWI700180B (en) * 2013-12-11 2020-08-01 日商凸版印刷股份有限公司 Laminated body and gas barrier film
JP6330316B2 (en) * 2013-12-19 2018-05-30 凸版印刷株式会社 Laminated body, barrier film, and production method thereof
JP2015132007A (en) * 2014-01-15 2015-07-23 凸版印刷株式会社 Method and apparatus for manufacturing laminate
CN106255591A (en) * 2014-03-04 2016-12-21 东洋制罐集团控股株式会社 Barrier laminate
JP2015178231A (en) * 2014-03-19 2015-10-08 東洋製罐グループホールディングス株式会社 Gas-barrier laminated structure
JP2015166170A (en) * 2014-03-04 2015-09-24 東洋製罐グループホールディングス株式会社 gas barrier laminate
JP6442874B2 (en) * 2014-05-30 2018-12-26 凸版印刷株式会社 LAMINATE MANUFACTURING METHOD AND LAMINATE MANUFACTURING DEVICE
SG11201609653SA (en) * 2014-06-13 2016-12-29 Basf Coatings Gmbh Process for producing organic-inorganic laminates
EP3176284B1 (en) * 2014-07-29 2021-03-10 Toppan Printing Co., Ltd. Laminate body and manufacturing method thereof, and gas barrier film and manufacturing method thereof
JP6554810B2 (en) * 2015-02-16 2019-08-07 凸版印刷株式会社 LAMINATE, MANUFACTURING METHOD THEREOF, AND GAS BARRIER FILM
JP6524702B2 (en) * 2015-02-26 2019-06-05 凸版印刷株式会社 Process for producing gas barrier film and gas barrier film
JP5906507B1 (en) * 2015-02-27 2016-04-20 株式会社昭和真空 Multilayer-coated resin substrate and method for producing the same
CN107428126B (en) * 2015-04-16 2020-11-03 凸版印刷株式会社 Laminate and gas barrier film
JP6657588B2 (en) * 2015-04-17 2020-03-04 凸版印刷株式会社 Laminated body and method for producing the same
DE102015122024A1 (en) * 2015-12-16 2017-06-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. A method for producing a composite layer consisting of a plastic film and a layer deposited thereon
EP3398769A4 (en) 2015-12-28 2019-12-18 Toppan Printing Co., Ltd. Laminate and method for manufacturing same, gas barrier film and method for manufacturing same, and organic light-emitting element
JP6849874B2 (en) * 2016-07-27 2021-03-31 株式会社Flosfia Manufacturing method of laminated structure
JP6834230B2 (en) * 2016-08-05 2021-02-24 大日本印刷株式会社 Barrier film
JP6944664B2 (en) * 2016-08-05 2021-10-06 大日本印刷株式会社 Barrier film
WO2018056401A1 (en) * 2016-09-23 2018-03-29 凸版印刷株式会社 Gas barrier optical film and organic el display
WO2019151495A1 (en) * 2018-02-02 2019-08-08 凸版印刷株式会社 Gas-barrier film and manufacturing method therefor
US11508937B2 (en) 2018-04-17 2022-11-22 Lg Chem, Ltd. Light-diffusing barrier film
CN109442101B (en) * 2018-10-08 2024-03-01 上海伟星新型建材有限公司 Oxygen-blocking pipe with outer layer hydrophobic function
JP6550198B1 (en) * 2019-02-28 2019-07-24 株式会社アドマップ SiC film structure
JP7221758B2 (en) * 2019-03-28 2023-02-14 東レエンジニアリング株式会社 Film forming apparatus and film forming method
JP2021172841A (en) * 2020-04-22 2021-11-01 東京エレクトロン株式会社 Film deposition method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1713983A (en) * 2002-11-22 2005-12-28 凸版印刷株式会社 Gas barrier laminate film
CN101065240A (en) * 2005-09-27 2007-10-31 凸版印刷株式会社 Gas barrier laminated film
CN102007173A (en) * 2008-04-17 2011-04-06 杜邦帝人薄膜美国有限公司 Coated and planarised polymeric films

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004204366A (en) * 2002-12-24 2004-07-22 Toppan Printing Co Ltd Moisture-proof paper and packaging paper, packaging bag or paper container using the same
WO2004105149A1 (en) 2003-05-16 2004-12-02 E.I. Dupont De Nemours And Company Barrier films for plastic substrates fabricated by atomic layer deposition
US20050172897A1 (en) 2004-02-09 2005-08-11 Frank Jansen Barrier layer process and arrangement
JP2007090803A (en) * 2005-09-30 2007-04-12 Fujifilm Corp Gas barrier film, and picture display element and organic electroluminescent element using the film
JP4954574B2 (en) 2006-03-02 2012-06-20 日東電工株式会社 Transparent gas barrier film manufacturing method and transparent gas barrier film manufacturing apparatus
WO2008029733A1 (en) * 2006-09-08 2008-03-13 Toppan Printing Co., Ltd. Multilayer body
JP2009010269A (en) * 2007-06-29 2009-01-15 Toppan Printing Co Ltd Rear face protection sheet for solar cell module, and solar cell module using the same
JP5092624B2 (en) * 2007-08-24 2012-12-05 大日本印刷株式会社 Method and apparatus for producing gas barrier film
DE102008048472A1 (en) * 2008-09-23 2010-03-25 Osram Opto Semiconductors Gmbh Barrier layer-encapsulated electronic component, e.g. LED, is obtained by successively applying layers by plasma-less atomic layer deposition and plasma-enhanced chemical vapor deposition
TWI388078B (en) * 2008-01-30 2013-03-01 Osram Opto Semiconductors Gmbh Method for manufacturing electronic components and electronic components
JP5309638B2 (en) * 2008-03-21 2013-10-09 Ｔｄｋ株式会社 Electronic components
JP2010000743A (en) * 2008-06-23 2010-01-07 Toppan Printing Co Ltd Gas barrier laminate
JP2010016286A (en) * 2008-07-07 2010-01-21 Toppan Printing Co Ltd Sheet for sealing backside of solar battery
JP5776132B2 (en) * 2009-04-03 2015-09-09 凸版印刷株式会社 Deposition equipment
JP2011165903A (en) 2010-02-10 2011-08-25 Rohm Co Ltd Semiconductor module and method of manufacturing the same
JP5668294B2 (en) * 2010-02-23 2015-02-12 凸版印刷株式会社 Gas barrier film and manufacturing method thereof
CN103732393B (en) * 2011-07-28 2016-10-05 凸版印刷株式会社 Duplexer, gas barrier film, the manufacture method of duplexer and laminated body producing device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1713983A (en) * 2002-11-22 2005-12-28 凸版印刷株式会社 Gas barrier laminate film
CN101065240A (en) * 2005-09-27 2007-10-31 凸版印刷株式会社 Gas barrier laminated film
CN102007173A (en) * 2008-04-17 2011-04-06 杜邦帝人薄膜美国有限公司 Coated and planarised polymeric films

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